Asymmetric Tetraprotonation of γ‐[(SiO₄)W₁₀O₃₂]⁸⁻ Triggers a Catalytic Epoxidation Reaction: Perspectives in the Assignment of the Active Catalyst

Water in the lagoon: A fast catalytic epoxidation of both terminal and internal double bonds was promoted by the regioselective tetraprotonation of the polyoxometalate γ-[(SiO4)W10O32]8− (see picture), which leads to the localization of two water molecules on the reactive lacunary site. This mechanism was supported by evidence from kinetic, spectroscopic, and computational studies.